FLUORINATED ACETYLENES .12. REACTION OF 3,3,3-TRIFLUOROPROPYNYL-LITHIUM WITH BENZIL AND ALPHA-HALOACETOPHENONES

被引:3
作者
BARLOW, MG [1 ]
TAJAMMAL, S [1 ]
TIPPING, AE [1 ]
机构
[1] UNIV MANCHESTER,INST SCI & TECHNOL,DEPT CHEM,MANCHESTER M60 1QD,LANCS,ENGLAND
关键词
D O I
10.1016/S0022-1139(00)80404-2
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Treatment of 3,3,3-trifluoropropynyl-lithium (4) with benzil (2:1 molar ratio) in diethyl ether at -50-degrees-C, followed by addition of an excess of benzoyl chloride, affords 1-benzoyl-5-benzoyloxy-5-phenyl-2,3-bis(trifluoromethyl)cyclopenta-1,3-diene (11) (61%) and the 1,4-dialkynyl ester (CF3C=C)2CPhO2CPh (1b) (8%). Similar reaction of the salt 4 with alpha-chloroacetophenone (2:1 molar ratio) in diethyl ether at -50-degrees-C, followed by addition of a slight excess of benzoyl chloride, gives the ester CF3C=CCPh(CH2Cl)O2CPh (14a) (55%) and a compound considered to be 2,5-diphenyl-2,5-bis(3,3,3-trifluoropropynyl)-1,4-dioxan (15) (30%). Under the same conditions, alpha-bromoacetophenone yields the corresponding bromo ester CF3C=CCPh(CH2Br)O2CPh (14b) (39%), 2-phenyl-2-(3,3,3-trifluoropropynyl)oxirane (16) (25%) and the dialkynyl ester (1b) (7%). The oxirane 16, conveniently prepared (51%) by treatment of salt 4 with the bromoketone (1:1 molar ratio) in THF at -60-degrees-C, on reaction with lithium phenylacetylide followed by addition of benzoyl chloride (c. 1:1:1 molar ratio) in THF at -60-degrees-C gives a compound identified as 2-phenyl-2-(1-phenyl-5,5,5-trifluoropent-3-en-1-yn-3-yl)oxirane (17) or possibly 2-phenyl-2-(3-phenylprop-2-yn-1-yl)-3-(2,2,2-trifluoroethylidene)oxirane (18) in 28% yield.
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页码:139 / 149
页数:11
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